Method of making a cyclic guanidine from a guanidinium salt and a weak acid and coating compositions containing the same

ABSTRACT

The present invention is directed to a method for preparing a cyclic guanidine comprising reacting (i) a guanidinium, (ii) a polyamine, and (iii) a weak acid. The present invention is also directed to a coating composition comprising the cyclic guanidine.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to a method for producing a cyclic guanidine and its use in coating compositions.

2. Background Information

Bicyclic guanidines, such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), have chemical activities which make them valuable catalysts for a number of chemical reactions. Published methods for synthesizing bicyclic guanidines, however, are often complicated, involving the use of a multistep synthesis process, and/or require the use of extremely hazardous or prohibitively expensive materials. A method for producing a cyclic guanidine that reduces and/or eliminates hazardous waste streams as well as the need for using hazardous and/or costly raw materials is therefore desired.

SUMMARY OF THE INVENTION

The present invention is directed to a method for preparing a cyclic guanidine comprising reacting (i) a guanidinium salt, (ii) a polyamine, and (iii) a weak acid. The present invention is also directed to a coating composition comprising the cyclic guanidine.

The present invention is also directed to a method of making a resin comprising reacting the following ingredients: (a) a cyclic guanidine reaction product of: (i) a guanidinium salt, (ii) a polyamine, and (iii) a weak acid; (b) an amine; and (c) an epoxy compound.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear. When referring to any numerical range of values, such ranges are understood to include each and every number and/or fraction between the stated range minimum and maximum. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. As employed herein, the term “number” means one or an integer greater than one.

As used herein, plural phrases or terms encompasses their singular counterparts and vice versa, unless specifically stated otherwise. By way of illustration, and not limitation, although reference is made herein to “a” cyclic guanidine reaction product, “an” amine, “a” polyamine; “an” epoxy compound, “a” guanidinium salt; a plurality of these materials may be used in the present invention. As used herein, “plurality” means two or more.

As used herein, “includes” and like terms means “including without limitation.”

As used herein, the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances.

As used herein, “molecular weight” means weight average molecular weight (Mw) as determined by Gel Permeation Chromatography.

As used herein, the term “cure” refers to a process wherein the crosslinkable components of a coating are at least partially crosslinked. In certain embodiments, the crosslink density of the crosslinkable components (i.e., the degree of crosslinking) ranges from 5% to 100%, such as 35% to 85%, or, in some cases, 50% to 85% of complete crosslinking. One skilled in the art will understand that the presence and degree of crosslinking, i.e., the crosslink density, can be determined by a variety of methods, such as dynamic mechanical thermal analysis (DMTA) using a Polymer Laboratories MK III DMTA analyzer conducted under nitrogen.

Reference to any monomer(s) herein refers generally to a monomer that can be polymerized with another polymerizable component such as another monomer or polymer. Unless otherwise indicated, it should be appreciated that once the monomer components react with one another to form a compound, the compound will comprise the residues of such monomer components.

As used herein, “weak acid” means a compound with 5.0<pKa<13.5 as measured in water. For example the pKa of a weak acid can range from 5.5<pKa<10.0.

As used herein, “cyclic guanidine” comprises structures (I) through (V) as well as the salts of such compounds:

wherein each of R1, R2, R3, R4, R5 (i.e., substituents of structure (I)) can comprise hydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, a polymeric structure, or together can form a cycloalkyl, aryl, or an aromatic structure, and wherein R1, R2, R3, R4, and R5 can be the same or different. As used herein, “(cyclo)alkyl” refers to both alkyl and cycloalkyl. It will be understood that in the present invention, at least two adjacent R groups are connected to form a cyclic moiety, such as the rings in structures (II)-(V) below.

In some embodiments, the double bond between the carbon atom and the nitrogen atom that is depicted in structure (I) may be located between the carbon atom and another nitrogen atom of structure (I). Accordingly, the various substituents of structure (I) may be attached to different nitrogens depending on where the double bond is located within the structure.

In certain embodiments, the cyclic guanidine comprises the guanidine of structure (I) wherein two or more R groups of structure (I) together form one or more rings. In other words, in some embodiments, the cyclic guanidine comprises ≧1 ring. For example, the cyclic guanidine can either be a monocyclic guanidine (1 ring) as depicted in structures (II) and/or (III) below, or the cyclic guanidine can be polycyclic (≧2 rings) as depicted in structures (IV) and (V) below.

Each substituent of structures (II) and/or (III), R1-R7, can comprise hydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, a polymeric structure, or together can form a cycloalkyl, aryl, or an aromatic structure, and wherein R1-R7 can be the same or different. Similarly, each substituent of structures (IV) and (V), R1-R9, can be hydrogen, alkyl, aryl, aromatic, organometallic, a polymeric structure, or together can form a cycloalkyl, aryl, or an aromatic structure, and wherein R1-R9 can be the same or different. Moreover, in some embodiments of structures (II) and/or (III), certain combinations of R1-R7 may be part of the same ring structure. For example, R1 and R7 of structure (II) may form part of a single ring structure. Moreover, in some embodiments, it will be understood that any combination of substituents (R1-R7 of structures (II) and/or (III) as well as R1-R9 of structures (IV) and/or (V)) can be chosen so long as the substituents do not substantially interfere with the catalytic activity of the cyclic guanidine.

In certain embodiments, each ring in the cyclic guanidine is comprised of ≧5-members. For instance, the cyclic guanidine may be a 5-member ring, a 6-member ring, or a 7-member ring. As used herein, the term “member” refers to an atom located in a ring structure. Accordingly, a 5-member ring will have 5 atoms in the ring structure (“n” and/or “m”=1 in structures (II)-(V)), a 6-member ring will have 6 atoms in the ring structure (“n” and/or “m”=2 in structures (II)-(V)), and a 7-member ring will have 7 atoms in the ring structure (“n” and/or “m”=3 in structures (II)-(V)). If the cyclic guanidine is comprised of ≧2 rings (e.g., structures (IV) and (V)), the number of members in each ring of the cyclic guanidine can either be the same or different. For example, one ring may be a five-member ring while the other ring may be a six-member ring. If the cyclic guanidine is comprised of ≧3 rings, then in addition to the combinations cited in the preceding sentence, the number of members in a first ring of the cyclic guanidine can be different from the number of members in any other ring of the cyclic guanidine.

In certain embodiments, the nitrogen atoms of structures (II)-(V) can further have additional atoms attached thereto. Moreover, in some embodiments, the cyclic guanidine can either be substituted or unsubstituted. For example, as used herein in conjunction with the cyclic guanidine, “substituted”, in certain embodiments, refers to a cyclic guanidine wherein R5, R6, and/or R7 of structures (II) and/or (III) and/or R9 of structures (IV) and/or (V) is not hydrogen. As used herein in conjunction with the cyclic guanidine, “unsubstituted”, in certain embodiments, refers to a cyclic guanidine wherein R1-R7 of structures (II) and/or (III) and/or R1-R9 of structures (IV) and/or (V) is hydrogen. In some embodiments, the substituted cyclic guanidine is 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Method of Making Cyclic Guanidine

As stated above, the present invention is directed to a method making a cyclic guanidine. There may be several advantages that may be realized when using the method described herein when compared to other methods known in the art. For example, the method of the present invention could eliminate and/or reduce the amount of waste produced by the disclosed process thereby eliminating and/or reducing the need to manage potential waste streams.

The method of the present invention comprises: reacting (i) a guanidinium salt; (ii) a polyamine; and (iii) a weak acid thereby forming a cyclic guanidine. All three of these components are added into a suitable reaction vessel and the reaction is conducted at a temperature ranging from 75° C. to 200° C., such as 100° C. to 120° C., or 120° C. to 140° C., or 140° C. to 160° C., or 150° C. to 180° C., for a time period ranging from 60 to 180 minutes, such as 90 minutes to 150 minutes or 110 minutes to 130 minutes. While water and/or ammonia are typical by-products of the disclosed process, in certain embodiments, the ammonia can be collected and recycled for use in the formation of additional polyamine thereby eliminating a potential waste stream. Alternatively, if the ammonia is not to be recycled, it can be scrubbed and discarded from the process using techniques that are known in the art.

Suitable guanidinium salts that may be used in the present invention include, without limitation, guanidinium carbonate, guanidinium sulfide, guanidine thiocyanate, or combinations thereof. These compounds may be derived from an acid having a pKa of 3<pKa<13.5. Additionally, the acid itself may be volatile or have the ability to dissociate into a volatile compound such as CO₂ and/or water. In certain embodiments, the guanidinium salt does not include guanidinium halide (e.g., guanidinium hydrochloride), guanidinium mesylate, guanidinium sulfate, guanidinium phosphate, or guanidinium nitrate.

Suitable polyamines that may be used within the present invention include, without limitation, any polyamine comprising a 1,5,9-triaza nonane moiety. In certain embodiments, the polyamine comprises dipropylene triamine, diethylene triamine, triethylene tetramine, tripropylene tetramine, or combinations thereof.

Suitable weak acids that may be used in connection with the present invention include, without limitation, phenol, thiol, sulfide, bicarbonate, carbonate, polymerization reaction products of any of the foregoing, or combinations thereof. In certain embodiments, these materials may be polyfunctional. Suitable phenols include, without limitation, bisphenol A, ^(t)butyl phenol, nonylphenol, resorcinol, polymerization reaction products of any of the foregoing, or combinations thereof.

One embodiment of the reaction process is depicted in Equation (I) below:

wherein H—X comprises a weak acid and R comprises H or a carbon containing substituent.

Method of Making a Polymeric Resin

The present invention is further directed to a method of making a polymeric resin. As will be discussed in greater detail below, the polymeric resin may be used, for example, in an electrodepositable (electrodeposition) coating composition such as those described in U.S. Patent Pub. No. 2009/0042060, which is incorporated herein by reference.

The method of the present invention comprises reacting various ingredients in order to form the polymeric resin. One of the ingredients used in the method of the present invention is (a) the cyclic guanidine reaction product of (i) a guanidinium salt, (ii) a polyamine, and (iii) a weak acid. Other ingredients that can be reacted with component (a) include, without limitation, (b) an amine, and (c) an epoxy compound. In some embodiments, after components (a), (b), and (c) are added to a suitable reaction vessel, the reaction is conducted at a temperature ranging from 75° C. to 200° C., such as 100° C. to 120° C., or 120° C. to 140° C., or 140° C. to 160° C., or 150° C. to 180° C., for a time period ranging from 60 to 180 minutes, such as 90 minutes to 150 minutes or 110 minutes to 130 minutes. In certain embodiments, components (a), (b), and (c) are added to a single reaction vessel. Accordingly, in some embodiments, the method disclosed herein can be described as a two-step, single reaction vessel (reaction pot), reaction process. For example, component (c) may be formed by polymerizing various monomers such as bisphenol A diglycidyl ether and bisphenol A. After component (c) is formed, components (a) and (b) are added to the reaction vessel and the reaction is allowed to continue until the desired reaction product is formed. While components (a) and (b) may be added simultaneously, in certain embodiments, these components are added in a sequential order.

The method of making component (a), as well as the various compounds that may be used as components (i), (ii), and (iii), is described in detail in the preceding section entitled “Method of Making Cyclic Guanidine”.

Suitable amines that may used as component (b) not only include the various polyamines described as component (ii) in the preceding paragraphs, but mono-functional amines as well. Suitable mono-functional amines include, without limitation, N-methylethanol amine, diethanol amine, or combinations thereof. Other amines that may be used include, without limitation, 3-dimethylaminopropyl amine, the reaction product of diethylene triamine bis-ketamine and methyl isobutyl ketone, as well as other amines capable of terminating or extending an epoxy resin can be used.

Suitable epoxy compounds that may be used as component (c) include, without limitation, neodecanoic acid glycidyl ester, 2-ethylhexy glycidyl ether, phenyl glycidyl ether, ethylene oxide, propylene oxide, butylene oxide, epoxidized α-olefins, styrene oxide, and glycidyl ethers of lower mono-alcohols such as butyl glycidyl ether and phenyl glycidyl ether. Glycidyl esters of neoacids such as glycidyl neodecanoate or glycidyl pivalate may be used so long as they can be protected from strong acid-forming hydrolysis when added to the cyclic guanidine. In certain embodiments, the epoxy compound is, itself, a polymeric compound. Examples of such a polymeric compound are the epoxy resins that are typically used in cationic electrodepositable coating compositions and which are known in the art.

In some embodiments, a sufficient amount of a polymeric epoxy compound is used so that a majority of the weak acid component (e.g., phenol), the cyclic guanidine, and any additional amines are reacted away. One embodiment of this reaction process is depicted in Equation (III). In this equation, the cyclic guanidine is formed via the process described in the section above entitled “Method of Making Cyclic Guanidine”.

wherein R comprises H, C, N, chalcogen, halogen, or combinations thereof.

In some embodiments, the method can further comprise reacting components (a), (b), (c), and (d) a polyamine (poly-functional amine). In certain embodiments, all of these components are added to a single reaction vessel. For example, component (c) may be formed by polymerizing various monomers such as bisphenol A diglycidyl ether and bisphenol A. After component (c) is formed, components (a), (b), and (d) are added to the reaction vessel and the reaction is allowed to continue until the desired reaction product is formed. While components (a), (b), and (d) may be added simultaneously, in certain embodiments, these components are added in a sequential order. The polyamine used as component (d) can be the same or different from the polyamines described as component (ii) and/or component (b) in the preceding paragraphs. For example, in certain embodiments, a mono-functional amine may be used as component (b) while a polyamine is used as component (d).

In some embodiments, the polymeric resin formed from the method disclosed herein comprises hydroxyl functionality. Therefore, in some embodiments, the polymeric resin may be modified or chain-extended with an isocyanate. Suitable isocyanates that may be used include, without limitation, mono or polyisocyanate compounds that could be used to functionalize or chain extend alcohol functional compounds while maintaining the catalytic activity of the cyclic guanidine. For example, methyl isocyanate, butyl isocyanate, α,α-dimethyl metaisopropenyl benzyl isocyanate (m-TMI), hexamethylene diisocyanate (HDI) isophorone diisocyanate (IPDI), 4,4′-diisocyanatodicyclohexyl methane, toluene diisocyanate (TDI), methylene diphenyl isocyanate (MDI), NCO-functional polymeric versions of any of the foregoing, or combinations thereof, may be used as the isocyanate.

Coating Composition

The present invention is also directed to a coating composition comprising the cyclic guanidine and/or the polymeric resin described in the preceding paragraphs. In some embodiments, the coating composition is an electrodepositable coating composition. The method of the present invention may provide several advantages over conventional methods of making an electrodepositable coating composition. For instance, the present invention allows for the formation of a polymeric resin in a single step as opposed to other methods that require a two step process. This is accomplished due to the fact that unwanted by-products, such as TBD salts of strong acids, are not produced via the method disclosed herein and, therefore, further processing of the reaction product to render the base free is not necessary. In contrast, conventional methods of making the resin disclosed herein require multiple steps, such as isolation and filtering steps, due to the need of having to address the various by-products that arise via those methods, such as metal salts.

In general, an electrodepositable coating composition is made by dispersing a first and second component in an aqueous solution thereby forming the electrodepositable coating composition. A suitable aqueous solution into which the components may be dispersed is water, such as deionized water.

In general, the first component, which can be described as the main vehicle (“clear resin feed”), a film-forming polymer or resin, such as an active hydrogen-containing ionic salt group containing resin, and a curing agent (crosslinking agent) that is capable of reacting with the film-forming polymer. The first component may also comprise any additional water-dispersible, non-pigmented components (e.g., catalysts, hindered amine light stabilizers). The film-forming polymer can be the polymeric resin disclosed above or it can be a combination of the polymeric resin and another film-forming polymer. In addition to the polymeric resin of the present invention, a wide variety of film-forming polymers can be used so long as the polymers are “water dispersible.” As used herein, “water dispersible” means that a material is adapted to be solubilized, dispersed, and/or emulsified in water. Examples of film-forming polymers suitable for use in the present invention, without limitation, polymers derived from a polyepoxide, an acrylic, a polyurethane, a polyester, or combinations thereof. In certain embodiments, the film-forming polymer can comprise functional groups. As used herein, “functional groups” or “reactive functional groups” means hydroxyl, carboxyl, carbamate, epoxy, isocyanate, aceto acetate, amine-salt, mercaptan, or combinations thereof. The film-forming polymers used in the present invention are also ionic in nature. Accordingly, in some embodiments, the film-forming polymer is cationic. In other words, the film-forming polymer comprises cationic salt groups, generally prepared by neutralizing a functional group on the film-forming polymer with an acid, which enables the film-forming polymer to be electrodeposited onto a cathode. For example, in some embodiments, a film-forming cationic polymer can be derived by reacting a polyepoxide containing polymer with a cationic salt group former. As used herein, “cationic salt group former” means a material that is reactive with epoxy groups and which can be acidified before, during, or after reaction with the epoxy groups to form cationic salt groups. Suitable materials that can be used as the cationic salt group former include, without limitation, amines such as primary or secondary amines, which can be acidified after reaction with the epoxy groups to form amine salt groups, or tertiary amines, which can be acidified prior to reaction with the epoxy groups and after reaction with the epoxy groups, form quaternary ammonium salt groups. Examples of other cationic salt group formers are TBD and sulfides (e.g., thioethers) which can be mixed with acid prior to reaction with the epoxy groups and form ternary sulfonium salt groups upon subsequent reaction with the epoxy groups.

As stated above, the first component also comprises a curing agent that is reactive towards that film-forming resin described in the preceding paragraph. For example, the film-forming agent may comprise moieties that are reactive with the functional groups of the film-forming polymer. Suitable crosslinking agents that may be used include, without limitation, aminoplasts, polyisocyanates (including blocked isocyanates), polyepoxides, beta-hydroxyalkylamides, polyacids, anhydrides, organometallic acid-functional materials, polyamines, polyamides, cyclic carbonates, siloxanes, or combinations thereof. In some embodiments, the curing agent can comprise from 30 weight % to 40 weight % based on the total resin solids of the electrodepositable coating composition.

The first component may further comprise a curing catalyst that may be used to catalyze the reaction between the crosslinking agent and the film-forming polymer. In certain embodiments, the cyclic guanidine disclosed herein may act as a curing catalyst. Accordingly, in some embodiments, the polymeric resin, which contains the cyclic guanidine, can be self-catalyzing by maintaining the catalytic activity of the cyclic guanidine moiety. One advantage that might be derived from using the polymeric resin in a coating composition, such as an electrodepositable coating composition, is that additional curing catalysts may not be needed in order to catalyze the curing reaction since the polymeric resin itself can catalyze the reaction. Alternatively, if other curing catalysts are used in combination with the polymeric resin, it might be possible to reduce the amount of these other catalysts in the composition since the polymeric resin already comprises a catalytic moiety.

Examples of the other curing catalysts that may be used in the present invention include, without limitation, organotin compounds (e.g., dibutyltin oxide, dioctyltin oxide) and salts thereof (e.g., dibutyltin diacetate); other metal oxides (e.g., oxides of cerium, zirconium and/or bismuth) and salts thereof (e.g., bismuth sulfamate and/or bismuth lactate), or combinations thereof.

In general, the second component, which can be described as the grind vehicle (“pigment paste”), comprises a pigment (e.g., titanium dioxide, carbon black), a water-dispersible grind resin that comprises a polymer, which can be the same or different from the film-forming polymer described above, and, optionally, additives such as catalysts (e.g., the other catalysts described in the preceding paragraph), antioxidants, biocides, defoamers, surfactants, wetting agents, dispersing aids, clays, hindered amine light stabilizers, UV light absorbers and stabilizers, a stabilizing agent, or combinations thereof. All of these materials are known to those skilled in the art.

While the preceding paragraphs described the cyclic guanidine disclosed herein as being in the first component, the cyclic guanidine can also be incorporated into the second component and/or post added to the electrodepositable coating composition after the first and second components have been dispersed in the aqueous solution. Accordingly, depending on the user's preference, the cyclic guanidine can be incorporated into any of the components used to make the electrodepositable coating composition.

Coating System

The coating composition comprising the cyclic guanidine and/or polymeric resin of the present invention may be applied alone or as part of a coating system that can be deposited onto a number of different substrates. The coating system typically comprises a number of coating layers. A coating layer is typically formed when a coating composition that is deposited onto the substrate is substantially cured by methods known in the art (e.g., by thermal heating).

Suitable substrates that can be coated with the electrodepositable coating composition of the present invention include, without limitation, metal substrates, metal alloy substrates, and/or substrates that have been metallized, such as nickel plated plastic. In some embodiments, the metal or metal alloy can be aluminum and/or steel. For example, the steel substrate could be cold rolled steel, electrogalvanized steel, and hot dipped galvanized steel. Moreover, in some embodiments, the substrate may comprise a portion of a vehicle such as a vehicular body (e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, and/or roof) and/or a vehicular frame. As used herein, “vehicle” or variations thereof includes, but is not limited to, civilian, commercial, and military land vehicles such as cars, motorcycles, and trucks. It will also be understood that, in some embodiments, the substrate may be pretreated with a pretreatment solution, such as a zinc phosphate solution as described in U.S. Pat. Nos. 4,793,867 and 5,588,989. Alternatively, in other embodiments, the substrate is not pretreated with a pretreatment solution prior to coating the substrate with the coating composition described herein.

In certain embodiments, the coating composition is an electrodepositable coating composition comprising the cyclic guanidine and/or polymeric resin described above. The electrodepositable coating composition may be applied over a bare (i.e., non-pretreated) substrate or it can be applied to a substrate that has been pretreated. After the electrodepositable coating composition is cured, a primer-surfacer coating composition is applied onto at least a portion of the electrodepositable coating composition. The primer-surfacer coating composition is typically applied to the electrodepositable coating layer and cured prior to a subsequent coating composition being applied over the primer-surfacer coating composition.

The primer-surfacer layer that results from the primer-surfacer coating composition serves to enhance chip resistance of the coating system as well as aid in the appearance of subsequently applied layers (e.g., color imparting coating composition and/or substantially clear coating composition). As used herein, “primer-surfacer” refers to a primer composition for use under a subsequently applied coating composition, and includes such materials as thermoplastic and/or crosslinking (e.g., thermosetting) film-forming resins generally known in the art of organic coating compositions. Suitable primers and primer-surfacer coating compositions include spray applied primers, as are known to those skilled in the art. Examples of suitable primers include several available from PPG Industries, Inc., Pittsburgh, Pa., as DPX-1791, DPX-1804, DSPX-1537, GPXH-5379, OPP-2645, PCV-70118, and 1177-225A. Another suitable primer-surfacer coating composition that can be utilized in the present invention is the primer-surfacer described in U.S. patent application Ser. No. 11/773,482, which is incorporated in its entirety herein by reference.

It should be noted that in some embodiments, the primer-surfacer coating composition is not used in the coating system. Therefore, a color-imparting basecoat coating composition can be applied directly onto the cured electrodepositable coating composition.

In some embodiments, a color-imparting coating composition (hereinafter, “basecoat”) is deposited onto at least a portion of the primer surfacer coating layer, if present. Any basecoat coating composition known in the art may be used in the present invention. It should be noted that these basecoat coating compositions typically comprise a colorant.

In certain embodiments, a substantially clear coating composition (hereinafter, “clearcoat”) is deposited onto at least a portion of the basecoat coating layer. As used herein, a “substantially clear” coating layer is substantially transparent and not opaque. In certain embodiments, the substantially clear coating composition can comprise a colorant but not in an amount such as to render the clear coating composition opaque (not substantially transparent) after it has been cured. Any clearcoat coating composition known in the art may be used in the present invention. For example, the clearcoat coating composition that is described in U.S. Pat. Nos. 5,989,642, 6,245,855, 6,387,519, and 7,005,472, which are incorporated in their entirety herein by reference, can be used in the coating system. In certain embodiments, the substantially clear coating composition can also comprise a particle, such as a silica particle, that is dispersed in the clearcoat coating composition (such as at the surface of the clearcoat coating composition after curing).

One or more of the coating compositions described herein can comprise colorants and/or other optional materials, which are known in the art of formulated surface coatings. As used herein, the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect to the composition. The colorant can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes (e.g., aluminum flakes). A single colorant or a mixture of two or more colorants can be used in the coating composition described herein.

Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated into the coatings by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.

Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black and mixtures thereof. The terms “pigment” and “colored filler” can be used interchangeably.

Example dyes include, but are not limited to, those that are solvent and/or aqueous based such as phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum and quinacridone.

Example tints include, but are not limited to, pigments dispersed in water-based or water miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions division of Eastman Chemical, Inc.

As noted above, the colorant can be in the form of a dispersion including, but not limited to, a nanoparticle dispersion. Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect. Nanoparticle dispersions can include colorants such as pigments or dyes having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Example nanoparticle dispersions and methods for making them are identified in U.S. Pat. No. 6,875,800, which is incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution). In order to minimize re-agglomeration of nanoparticles within the coating, a dispersion of resin-coated nanoparticles can be used. As used herein, a “dispersion of resin-coated nanoparticles” refers to a continuous phase in which discreet “composite microparticles”, which comprise a nanoparticle and a resin coating on the nanoparticle, is dispersed. Example dispersions of resin-coated nanoparticles and methods for making them are identified in U.S. Patent Application Publication 2005-0287348, filed Jun. 24, 2004, U.S. Provisional Application No. 60/482,167 filed Jun. 24, 2003, and U.S. patent application Ser. No. 11/337,062, filed Jan. 20, 2006, which is also incorporated herein by reference.

Example special effect compositions that may be used include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or color-change. Additional special effect compositions can provide other perceptible properties, such as opacity or texture. In a non-limiting embodiment, special effect compositions can produce a color shift, such that the color of the coating changes when the coating is viewed at different angles. Example color effect compositions are identified in U.S. Pat. No. 6,894,086, incorporated herein by reference. Additional color effect compositions can include transparent coated mica and/or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating, and/or any composition wherein interference results from a refractive index differential within the material and not because of the refractive index differential between the surface of the material and the air.

In certain non-limiting embodiments, a photosensitive composition and/or photochromic composition, which reversibly alters its color when exposed to one or more light sources, can be used in the coating composition described herein. Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition becomes excited, the molecular structure is changed and the altered structure exhibits a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic and/or photosensitive composition can return to a state of rest, in which the original color of the composition returns. In one non-limiting embodiment, the photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit a color in an excited state. Full color-change can appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds. Example photochromic and/or photosensitive compositions include photochromic dyes.

In a non-limiting embodiment, the photosensitive composition and/or photochromic composition can be associated with and/or at least partially bound to, such as by covalent bonding, a polymer and/or polymeric materials of a polymerizable component. In contrast to some coatings in which the photosensitive composition may migrate out of the coating and crystallize into the substrate, the photosensitive composition and/or photochromic composition associated with and/or at least partially bound to a polymer and/or polymerizable component in accordance with a non-limiting embodiment of the present invention, have minimal migration out of the coating. Example photosensitive compositions and/or photochromic compositions and methods for making them are identified in U.S. application Ser. No. 10/892,919, filed Jul. 16, 2004.

In general, the colorant can be present in any amount sufficient to impart the desired visual and/or color effect. The colorant may comprise from 1 to 65 weight percent of the present compositions, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the compositions.

One or more of the coating compositions described herein can comprise other optional materials well known in the art of formulated surface coatings, such as plasticizers, anti-oxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents such as bentonite clay, pigments, fillers, organic cosolvents, catalysts, including phosphonic acids and other customary auxiliaries.

In addition to the materials described above, one or more of the coating composition described above can also comprise an organic solvent. Suitable organic solvents that can be used in the coating composition include any of those listed in the preceding paragraphs as well as butyl acetate, xylene, methyl ethyl ketone, or combinations thereof.

It will be further appreciated that one or more of the coating compositions that form the various coating layers described herein can be either “one component” (“1K”), “two component” (“2K”), or even multi-component compositions. A 1K composition will be understood as referring to a composition wherein all of the coating components are maintained in the same container after manufacture, during storage, etc. A 2K composition or multi-component composition will be understood as referring to a composition wherein various components are maintained separately until just prior to application. A 1K or 2K coating composition can be applied to a substrate and cured by any conventional means, such as by heating, forced air, and the like.

The coating compositions that form the various coating layers described herein can be deposited or applied onto the substrate using any technique that is known in the art. For example, the coating compositions can be applied to the substrate by any of a variety of methods including, without limitation, spraying, brushing, dipping, and/or roll coating, among other methods. When a plurality of coating compositions are applied onto a substrate, it should be noted that one coating composition may be applied onto at least a portion of an underlying coating composition either after the underlying coating composition has been cured or prior to the underlying coating composition being cured. If the coating composition is applied onto an underlying coating composition that has not been cured, both coating compositions may be cured simultaneously.

The coating compositions may be cured using any technique known in the art such as, without limitation, thermal energy, infrared, ionizing or actinic radiation, or by any combination thereof. In certain embodiments, the curing operation can be carried out at temperatures ≧10° C. In other embodiments, the curing operation can be carried out at temperature ≦246° C. In certain embodiments, the curing operation can be carried out at temperatures ranging between any combination of values, which were recited in the preceding sentences, inclusive of the recited values. For example, the curing operation can be carried out at temperatures ranging from 120° C.-150° C. It should be noted, however, that lower or higher temperatures may be used as necessary to activate the curing mechanisms.

In certain embodiments, one or more of the coating compositions described herein is a low temperature, moisture curable coating compositions. As used herein, the term “low temperature, moisture curable” refers to coating compositions that, following application to a substrate, are capable of curing in the presence of ambient air, the air having a relative humidity of 10% to 100%, such as 25% to 80%, and a temperature in the range of −10° C. to 120° C., such as 5° C. to 80° C., in some cases 10° C. to 60° C. and, in yet other cases, 15° C. to 40° C.

The dry film thickness of the coating layers described herein can range from 0.1 micron to 500 microns. In other embodiments, the dry film thickness can be ≦125 microns, such as ≦80 microns. For example, the dry film thickness can range from 15 microns to 60 microns.

While specific embodiments of the invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the claims appended and any and all equivalents thereof.

EXAMPLES Example 1

Cyclic guanidine-BPA salt # Material Parts by Weight (g) 1 Guanidine carbonate 90.0 2 Deionized (DI) water 150.0 3 Bisphenol A 228.3 4 Butyl celloslove 235.0 5 Dipropylene triamine 131.2

Materials 1 and 2 were added to a round bottom flask equipped with a mechanical stirrer, reflux condenser, temperature probe and inert gas inlet. The mixture was then heated to 60° C. to ensure complete dissolution. Material 4 was then added, followed by material 3. The reflux condenser was replaced with a Dean-Stark trap, and the heterogeneous mixture was warmed to 101° C. 33 grams (g) of distillate was collected and the reaction became homogenous. Material 5 was then added and an exotherm ensued with a maximum temperature of 108° C. The mixture was then warmed to 165° C. while allowing water/butyl cellosolve to distill out. After the mixture reached 165° C., a small amount of xylenes was added to help remove water from the mixture. After 1.5 hours (h) at 165° C., the reaction was cooled. ¹³C NMR analysis is consistent with the bisphenol A salt of 1,5,7-triazebicyclo[4.4.0]dec-5-ene.

Cyclic guanidine-containing catalyst resin # Material Parts by Weight (g) 1 1:2 guanidine:BPA salt, 83% solids in butyl 80.0 cell, prepared as above 2 Methyl ethanol amine 9.6 3 EPON 828 107.8 4 DOWANOL PM 8.8 5 90% formic acid 12.5 6 DI water 608.9

Material 1 was warmed to 80° C. then charged to a 250 ml round bottomed flask equipped with a mechanical stirrer, reflux condenser, temperature probe and inert gas inlet. Materials 2, 3, and 4 were added and an immediate exotherm ensued which peaked at 122° C. in 10 min. External heat was then added and the mixture was brought to 130° C. and held at this temperature for 2.25 hour (“h” or “hr”). The thick resin was then dispersed into 5 and 6, which was heated to aid in dispersion. The final dispersion had a solids content of 17.6%, a meq acid of 0.204 and a meq base of 0.224 on resin solids.

Example 2

Material # Material Parts by Weight (g) 1 DER-732¹ 711 2 Bisphenol A 172 3 Benzyldimethyl amine 1.65 4 Butoxyethanol 58.8 5 JEFFAMINE D400² 184.7 6 EPON 828³ 19.1 7 Butoxyethanol 3.4 8 Deionized water 1047 9 Acetic Acid 19 10 Deionized water 1030 ¹Aliphatic epoxy resin available from Dow Chemical Co. ²Polyoxypropylene diamine available from Huntsman Corp. ³A difunctional bisphenol A/epichlorohydrin derived liquid epoxy resin available from Hexion Specialty Chemical

Material 1 and 2 were charged to a suitably equipped 3-liter round-bottomed flask. The mixture was heated to 130° C. and material 3 was added. The reaction mixture was held at 135° C. until the epoxide equivalent weight of the mixture was 1232. Material 4 was added and then the mixture is cooled to 95° C. Material 5 was added and the reaction held at 95° C. until the Gardner-Holdt viscosity of a sample of the resin diluted 50% solids in methoxy propanol was “H-J”. A mixture of material 6 and 7 was added and the mixture held until the Gardner-Holdt viscosity of a sample of the resin diluted to 50% solids in methoxy propanol is “Q-”. 989 g of this resin was poured into a mixture of material 8 and 9 and mixed for 30 minutes. 1030 g deionized water (material 10) was then added and mixed well. The final aqueous dispersion had a measured solids content of 30%.

Example 3

Material # Material Parts by Weight (g) 1 EPON 828¹ 1023 2 MACOL 98B² 365 3 Bisphenol A 297 4 2-Butoxyethanol 187.2 5 Benzyldimethylamine 1.4 6 Benzyldimethylamine 3.0 7 Diketimine³ 182.3 8 N-methylethanolamine 85.2 9 Acetic Acid 105.9 10 Deionized water 1065.9 11 Deionized water 735.9 12 Deionized water 1156.4 13 Deionized water 867.3 ¹A difunctional bisphenol A/epichlorohydrin derived liquid epoxy resin available from Hexion Specialty Chemical ²Bisphenol A ethoxylate of hydroxyl equivalent weight approximately 245 available from BASF Corp. ³MIBK diketimine of diethylene triamine at 72.7% in MIBK.

EPON 828, bisphenol A-ethylene oxide adduct, bisphenol A and 2-butoxyethanol were charged into a reaction vessel and heated under a nitrogen atmosphere to 125° C. The first portion of the benzyldimethylamine was added and the reaction allowed to exotherm to around 180° C. During the exotherm when the reaction reached 160° C., a one hour hold was started. After the peak exotherm the resin was allowed to cool back to 160° C., continuing the hold. After the hold the reaction was then cooled to 130° C. At 130° C. the second portion of benzyldimethylamine was added. The reaction was held at 130° C. until an extrapolated epoxy equivalent weight of 1070. At the expected epoxy equivalent weight, diketimine and N-methylethanolamine were added in succession and the mixture allowed to exotherm to around 150° C. At the peak exotherm a one hour hold was started while allowing the reaction to cool to 125° C. After the one hour hold the resin was dispersed in an aqueous medium consisting of acetic acid and the first portion of deionized water. The dispersion was later reduced with the second, third, and fourth portions of deionized water. The resulting cationic soap was vacuum striped until the methyl isobutyl ketone liberated by the hydrolysis of the diketime was less than 0.05%. The solids f the aqueous solution was adjusted to 26%.

Example 4

443 g of deionized water was then added to 2517 g of the above aqueous polymer solution. The mixture was heated to 70° C. under a nitrogen blanket. 44.8 g of an 85% solution of EPON 828 in mibk was then added over 15 minutes with agitation. 4.05 g of mibk was added as a rinse for the EPON 828 solution and the mixture held at 70° C. for 45 minutes. The mixture was heated to 90° C. over 70 minutes and held at this temperature for 3 hours with mixing. 337 g of deionized water was then added and the dispersion cooled to less than 35° C. and poured out. The measured solids content was 18.89%

Example 5

# Material Parts by Weight (g) 1 EPON 828¹ 533.2 2 nonyl phenol 19.1 3 bisphenol A 198.3 4 ethyltriphenyl phosphonium iodide 0.7 5 butoxy propanol 99.3 6 butoxy propanol 93.9 7 methoxy propanol 50.3 8 thiodiethanol 121.3 9 butoxy propanol 6.9 10 deionized water 32.1 11 dimethylol propionic acid 133.1 12 Deionized water 1100 13 Deionized water 790 ¹Diglycidyl ether of Bisphenol A commercially available from Resolution Chemical Co as Epon 828.

Materials 1 through 5 were charged to a suitably equipped flask and heated to 125° C. The mixture was allowed to exotherm to 175° C. and then held at 160-165° C. for 1 hr. After the 1 hr hold materials 6-7 were added. The mixture was cooled to 80° C. and materials 8-11 were added. The mixture was then held at 78° C. until the measured acid value was less than 2. When the acid value was less than 2, 1288.2 g of the resin was poured into 1100 g of deionized water (material 12) with stirring. The mixture was mixed for 30 minutes then material 13 was added and the mixture was mixed well.

Example 6

Material Description Parts by Weight (g) 1 Cationic resin¹ 25.85 2 Cationic resin from Example 5 30.6 3 Deionized water 32.55 4 Silica² 11 ¹Cationic resin from Example II of U.S. Pat. No. 4,007,154. ²Available from Evonik pigments as OK-607

Materials 1 through 3 were blended in an appropriate container for cowels dispersion. Material 4 was then added under high speed cowels dispersion. The pigment was dispersed then ground until a particle size, as measured by a Hegman gauge, of 12-14 microns was observed.

Example 7

Material Description Parts by Weight (g) 1 Cationic resin from Example 5 12.8 2 Cationic resin¹ 2.8 3 Deionized water 2.74 4 Ethylene glycol monobutyl ether 0.8 5 Titanium Dioxide² 21.1 6 Carbon Black 0.09 7 Tin Dioxide powder 0.20 8 Pigment paste from Example 6 55 9 Deionized Water 4.47 ¹Cationic resin from Example II of U.S. Pat. No. 4,007,154. ²Available from KRONOS as 2305 or DUPONT as R900 ³Printex 200 available from Evonik Pigments

Materials 1 through 4 were blended in a container appropriate for a cowels dispersion. Materials 5, 6, and 7 were then added under high speed cowels dispersion and the resulting pigment dispersion was held under high speed cowels dispersion for 20 minutes. The dispersion was then transferred to a Vertical mill equipped with 1-1.6 mm zircoa beads and milled until a particle size of 8-10 microns was observed (as measured by a Hegman gauge). The mill time was approximately 30 minutes. Material 8 was then blended into the resulting pigment dispersion under low shear and material 9 was added to bring the resulting pigment dispersion to a total solids of 45.31%.

Example 8

Parts by Weight (g) 1 LUPRANATE M20¹ 1340.00 2 dibutyltin dilaurate 1.00 3 methylisobutyl ketone 306.04 4 butyl Cellosolve 236.00 5 MACOL 98B² 246.50 6 methanol 225.60 TOTAL 2355.14 ¹Isocyanate available from BASF Corp. ²Bisphenol A ethoxylate of hydroxyl equivalent weight approximately 245 available from BASF Corp.

1, 2, and 3 were charged into a reaction vessel under a nitrogen atmosphere. Charge 4 was added over about 1 hour allowing the temperature to increase to 50° C. Charge 5 was then added slowly allowing the reaction mixture to exotherm to 65° C. The mixture was then held until the isocyanate equivalent weight was 304±10. The nitrogen flow was then stopped and charge 6 was added at a controlled rate allowing the reaction mixture to exotherm to a maximum of 100° C. The mixture was then held at 100° C. until the infrared spectrum indicated no residual isocyanate. The mixture had a measured solids content of 87%.

Example 9

Material # Material Parts by Weight (g) 1 EPON 828 553.2 2 Bisphenol A 238.9 3 MACOL 98B¹ 112.5 4 Methyl Isobutyl Ketone 18.5 5 Ethyl triphenyl phosphonium iodide 0.5 6 MACOL 98B¹ 36.9 7 Methyl Isobutyl Ketone 21.1 8 Crosslinker (Example 8) 1079.2 9 Diketimine² 51.3 10 Diethanol Amine 61.2 11 Formic Acid 28 12 Deionized Water 1355.1 13 Deionized Water 1049 14 Deionized Water 1200 ¹Bisphenol A ethoxylate of hydroxyl equivalent weight approximately 245 available from BASF Corp. ²MIBK diketimine of diethylene triamine at 72.7% in MIBK.

Materials 1 through 5 were charged sequentially into a 3 neck flask equipped with a mechanical stirrer, condenser nitrogen purge, temperature controller and a heating mantel. The reaction is allowed to exotherm, and is then held at 145 C for 2 hrs. Material 6 is then added and stirred for 15 minutes. Material 7 and 8 are added sequentially and allowed to stir for 15 minutes. Materials 9 and 10 are then added and the reaction is allowed to exotherm, and then is held at 125 C for 1 hr. The resulting cationic resin is then dispersed by adding the resin to a solution of materials 11 and 12 under agitation. The dispersion is allowed to stir for 30 minutes, then material 13 is added slowly and the dispersion is stirred for an additional 30 minutes. Material 14 is then added to reduce the resin to final solids. MIBK is then removed by heating to a temperature of 60-65° C. and vacuum distilling off 1200 grams of water/MIBK.

Example 10

Material # Description Parts by Weight (g) 1 2-butoxyethanol 31.26 2 SURFYNOL 104 31.26 3 Amine C¹ 32.46 4 75% Acetic acid in Water 5.01 ¹4,5-Dihydro-1H-Imidazole-1-ethanol available from Ciba Geigy

Materials 1 through 4 were blended sequentially.

Example 11

Parts by Weight (g) Material # Description Paint A Paint B 1 Cationic resin from Example 2 58.63 58.63 2 Cationic resin from Example 3 48.86 48.86 3 Propylene glycol Phenyl ether 8.79 8.79 4 Ethylene glycol hexyl ether 17.59 17.59 5 Mazon 1651¹ 15.39 15.39 6 Noramox C5² 2.26 2.26 7 Surfactant Blend from example 10 3.54 3.54 8 Cationic resin from Example 9 708.67 904.03 9 Cyclic guanidine-containing catalyst resin 461.82 0 from Example 1 10 Pigment Dispersion from Example 7 265.42 265.42 11 Deionized water 1475.48 1475.48 ¹Available from BASF corporation ²Available from CECA Prochinor

For each paint, materials 1 through 7 were blended sequentially and stirred 20 minutes. Materials 8 and 9 were blended in a separate 1 gallon container for 5 minutes. The blend of materials 1-7 was then added slowly to the blend of materials 8 and 9. Materials 10 and 11 were then added sequentially.

Panel Coating

For Examples 11A and 11B, each electrodepositable coating compositions were electrodeposited onto phosphated cold rolled steel under conditions sufficient to provide an electrodeposited film thickness of about 20 micrometers. The panels were then cured for 25 minutes at different temperatures and tested for cure by acetone double rubs using ASTM D5402-6 Method A with the following exceptions: Acetone was used rather than MIBK, no water cleaning of panel, 100 double rubs are done using a cheese cloth.

Note that paint 11A required ultrafiltration to coat well. The paint was initially ultrafiltered 20% by weight with the filtrate being replace with Deionized water. Paint 11A was additionally ultrafiltered as follows:

1) 1000 grams DI water was added to the bath,

2) 1000 grams of permeate was removed by ultrafiltration.

3) Repeat 2 times

Paint 11B did not require ultrafiltration to coat well.

Example 12

Panels coated with Paint 11A and 11B were tested for acetone resistance by the double rub method described above. Panels were cured in an electric oven and in a direct fired natural gas oven for the time and temperatures indicated in the attached chart. Up to 100 acetone double rubs were done on each panel. If the paint failed before 100 double rubs, the number of double rubs was noted in the chart.

Bake Paint 11A Paint 11B 210° C./25′Gas Pass - 100 Dar's/9+ Fail - 14 Dar's to metal 200° C./25′Gas Pass - 100 Dar's/9+ Fail - 5 Dar's to metal 170° C./25′Gas Fail - 28 Dar's to metal Fail - 2 Dar's to metal 160° C./25′Gas Did not test Fail - 1 Dar's to metal 210° C./25′Elec. Pass - 100 Dar's/9+ Fail - 50 Dar's/1 200° C./25′Elec. Pass - 100 Dar's/9+ Fail - 6 Dar's to metal 170° C./25′Elec. Pass - 100 Dar's/7+ Fail - 2 Dar's to metal 160° C./25′Elec. Fail - 12 Dar's to metal Fail - 1 Dar's to metal

As shown above, Paint 11A which has the cyclic guanidine catalyst resin showed good cure by solvent resistance for both gas and electric ovens. Paint 11B without any catalyst had poor cure (solvent resistance) for all cure conditions. 

What is claimed is:
 1. A method for preparing a cyclic guanidine comprising reacting (i) a guanidinium salt, (ii) a polyamine, and (iii) a weak acid.
 2. The method according to claim 1, wherein the (i) guanidinium salt comprises guanidinium carbonate.
 3. The method according to claim 1, wherein the (iii) weak acid comprises phenol, thiol, sulfide, bicarbonate, carbonate, polymerization reaction products of any of the foregoing compounds, or combinations thereof.
 4. The method according to claim 3, wherein the phenol comprises bisphenol A, T-butyl phenol, nonylphenol, polymerization reaction products of any of the foregoing compounds, or combinations thereof.
 5. The method according to claim 1, wherein the method is conducted at a temperature ranging from 75° C. to 200° C.
 6. The method according to claim 1, wherein the reaction product of (i), (ii), and (iii) is further reacted with an epoxy compound.
 7. The method according to claim 1, wherein the (ii) polyamine comprises dipropylene triamine.
 8. The method of claim 1, wherein the cyclic guanidine comprises a salt of the cyclic guanidine.
 9. A method of producing a polymeric resin comprising preparing (a) a cyclic guanidine by reacting (i) a guanidinium salt, (ii) a polyamine, and (iii) a weak acid, and reacting the following ingredients: the (a) cyclic guanidine; (b) an amine; and (c) an epoxy compound.
 10. The method according to claim 9, wherein the (c) epoxy compound comprises propylene oxide, butyl glycidyl ether, phenyl glycidyl ether, glycidyl neodecanoate, or combinations thereof.
 11. The method according to claim 9, wherein the (c) epoxy compound comprises a polyepoxide.
 12. The method according to claim 11, wherein the polyepoxide comprises a diglycidyl ether, polymerization reaction products of diglycidyl ethers, or combinations thereof.
 13. The method according to claim 12, wherein the diglycidyl ether comprises the diglycidyl ether of bisphenol A, polymerization reaction products of diglycidyl ether of bisphenol A, or combinations thereof.
 14. The method according to claim 9, wherein the amine is a monofunctional amine.
 15. The method according to claim 9, wherein the method further comprises reacting (d) a polyamine, wherein the polyamine can be the same or different from (ii).
 16. The method according to claim 9, wherein the (i) guanidinium salt comprises guanidinium carbonate.
 17. The method according to claim 9, wherein the (iii) weak acid comprises phenol, thiol, sulfide, bicarbonate, carbonate, polymerization reaction products of any of the foregoing compounds, or combinations thereof.
 18. The method according to claim 17, wherein the phenol comprises bisphenol A, T-butyl phenol, nonylphenol, polymerization reaction products of any of the foregoing compounds, or combinations thereof.
 19. The method according to claim 9, wherein the (ii) polyamine comprises dipropylene triamine.
 20. The method of claim 9, wherein the cyclic guanidine comprises a salt of the cyclic guanidine. 